EP0481332A2 - Körper aus gesintertem Feststoffelektrolyt - Google Patents

Körper aus gesintertem Feststoffelektrolyt Download PDF

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Publication number
EP0481332A2
EP0481332A2 EP91117124A EP91117124A EP0481332A2 EP 0481332 A2 EP0481332 A2 EP 0481332A2 EP 91117124 A EP91117124 A EP 91117124A EP 91117124 A EP91117124 A EP 91117124A EP 0481332 A2 EP0481332 A2 EP 0481332A2
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EP
European Patent Office
Prior art keywords
solid electrolyte
sintered body
yttria
resistance
zirconia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP91117124A
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English (en)
French (fr)
Other versions
EP0481332A3 (en
Inventor
Hidetoshi Nagamoto
Takao c/o Nissan Chemical Industries Ltd. Kaga
Yutaka c/o Nissan Chemical Ind. Ltd. Kimura
Masamichi c/o Nissan Chemical Ind. Ltd. Obitsu
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Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of EP0481332A2 publication Critical patent/EP0481332A2/de
Publication of EP0481332A3 publication Critical patent/EP0481332A3/en
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte composed of zirconia and yttria, and more particularly to a solid electrolyte sintered body composed of zirconia and yttria characterized in that temperature change of its electrical conductivity in high temperature range is small.
  • a Zirconia solid electrolyte mainly composed of zirconia has excellent merits that it has high oxygen ion conductivity and that electron conduction can be ignored in a wide range of oxygen partial pressure, and its importance as a solid electrolyte used for a solid oxide fuel cell or an oxygen sensor of exhaust gas of a car as been drawing an attention lately.
  • it is required to have not only high electrical conductivity and high ionic transference number but also to be chemically stable even in a low oxygen partial pressure of fuel electrode side and to have good characteristics as a ceramics in the homogeneity, closeness, mechanical strength and heat resistance.
  • cubic yttria stabilized zirconia (YSZ) that contains yttria by about 8 to 10 mol% shows the highest oxygen ion conductivity among stabilized zirconias and is stable thermally and chemically, so that it has been regarded to be the most important material in practical use and has been reported in various reports (such as "Japan Ceramic Society” vol. 89, No. 1, p. 14, 1981).
  • a tetragonal yttria partially stabilized zirconia (TZP) containing about 2 to 4 mol% of yttria which has been drawing an attention lately as a tough ceramic has excellent mechanical properties though its electrical conductivity is more or less lower than YSZ, so that its application to a solid oxide fuel cell is being considered.
  • the internal resistance determined by ohm resistances of the solid electrolyte, electrode materials, inter-connectors, and current collector or a resistance caused by electrode reactions is desired to be small as lessw as possible.
  • the oxygen ion conduction chracteristics of the conventional yttria stabilized zirconia (YSZ) cannot be said to be enough when it is used for a solid oxide fuel cell. It is because the contribution of the resistance of the solid electrolyte to the internal resistance is relataively large as same as the resistance caused by the electrode reactions, though it also depends on the structure of the fuel cell.
  • the improvement of the output and the conversion efficiency of the fuel cell is the most important subject in devleoping the solid oxide fuell cell. It is needless to say that how this is achieved with a fuel cell that can be fabricated in relatively low cost is the key whether the fuel cell is widely applied in industries.
  • the transmission of gas, such as oxygen and hydrogen, of the solid electrolyte must be able to be blocked. Therefore, the solid electrolyte needs to be fully close and to have a thickness that allows to block the gas transmission. Then, if the solid electrolyte is made to be fully close, its manufacturing method is also restricted. Moreover, the thinner the solid electrolyte, the more brittle it becomes against mechanical and thermal stresses, so that it must be considered to reinforce it using adequate supports from a certain point. Then it ends up adding another limit on the structure of the fuel cell. That is, there are limits practically in thinning the thickness of the solid electrolyte.
  • the higher temperature provides considerably a large merits.
  • peripheral materials including the electrode materials need to be able to sustain and to be used in such relatively high temperature range and thereby are subject to restriction in their selection.
  • the peripheral materials are also required to have a consistency in coefficient of thermal expansion with the solid electrolyte and a high electrical conductivity, beside the heat resistance. Due to that, it has become a considerably difficult technological problem to develop the peripheral materials that satisfy those requirements and are still in low cost.
  • the tetragonal yttria partially stabilized zirconia (TZP) is also being considered to be applied for the solid oxide fuel cell because it has excellent mechanical properties, though its electrical conductivity is more or less low comparing to YSZ. That is, TZP is considered to be able to sustain handling when it is incorporated in a unit in reality even when its thickness is considerably thinned to reduce its substantial resistance.
  • YSZ stabilized zirconia
  • the reality is that the ion conduction characteristics is not necessarily sufficient in the tetragonal partially stabilized zirconia in which about 3 mol% of yttria is added, in the cubic stabilized zirconia in which about 8 to 10 mol% of yttria is added or even in zirconia in which tetragonal and cubic stabilized zirconia are mixed with about 3 to 8 mol% of yttria.
  • the temperature dependency (activation energy) of the electrical conductivity of the solid electrolyte is small. For example, even when there is an inevitable temperature distribution within a fuel cell unit, its influence on the output characteristic is small. Also when the operation temperature of the fuel cell is lowered, the increase of the resistance of the solid electrolyte is small and the influence on the output characteristic is small. That is, when the operation temperature is lowered from 1000° C to 800° C for example, the increase of the resistance of the solid electrolyte becomes as follows depending on the value of the activation energy.
  • the increase is 2.77 times; when 0.7 eV, 3.29 times; when 0.8 eV, 3.89 times; and when 0.9 eV, 4.61 times. Then, considering based on 0.6 eV for example, the increase rate of the resistance when the activation energy is 0.7 eV, 0.8 eV and 0.9 eV is respectively 19 %, 40 % and 60 % increase.
  • peripheral materials In enables to design a fuel cell whose operation temperature is relatively low and to widen the selection of the peripheral materials. For example, metallic materials which are considered to be difficult to be used in around 1000° C can be considered as a candidate of the peripheral materials.
  • the improvement of the ion conduction characteristics of solid electrolyte material is a big plus in developing a solid oxide fuel cell.
  • a solid electrolyte sintered body that has a high electrical conductivity in high temperature range and whose temperature change of the electrical conductivity in the high temperature range is small can be obtained by using high purity easy-to-sinter raw material powder in which yttria, a stabilizer, is homogeneously solid-solubilized, by molding and sintering it in relatively low temperature to homogenize the distribution of the grain size of the sintered body obtained.
  • the present invention is concerned with a zirconia sintered body mainly composed of zirconia and yttria and more particularly with a solid electrolyte sintered body characterized in that the mol ratio of yttria and zirconia is in ranges of 2/98 to 10/90 and that temperature change of its electrical conductivity in high temperature range is small.
  • the solid electrolyte sintered body of the present invention can be obtained by using high purity easy-to-sinter raw material powder in which yttria, a stabilizer, is homogenously solid-solubilized in the range of 2/98 to 10/90 of mol ratio of yttria and zirconia, by molding and sintering it in relataively low temperature to homogenize the distribution of the grain size of the sintered body obtained.
  • the high purity zirconia raw material powder in the present invention is what the amount of impurities other than hafnium that normally comes together with zirconia and yttria used as the stabilizer is reduced.
  • the powder in which yttria is homogeneously solid-solubilized can be obtained by fully calcinating for a long time in high temperature in such known methods for producing the raw material powder as wet powder blending, coprecipitation, hydrolysis, alkoxide hydrolysis or a method disclosed in Japanese Patent Application Laid-Open No. 63-185821.
  • the preferable calcination tempeature is from 900 to 1100° C or more preferably from 950 to 1050° C or further from 1000 to 1050° C and the preferable calcination time is more than 2 hours in total, or more preferably more than 4 hours or further more than 8 hours.
  • the better method which is more effective is to calcinate plural times, for example, to calcinate 2 times for 6 hours or 3 times for 4 hours rather than 1 time for 12 hours.
  • the calcination temperature is higher than 1100° C, agglomeration of the powder particle becomes intense, though it depends on the production method of the powder, an it becomes difficult to make it agglomeration free by pulverizintg to make ease-to-sinter powder having less agglomeration.
  • the calcination temperature is lower than 900° c, it takes too much time for homogeneously solubilizing yttria and is not economical.
  • the calcination time is less than 2 hours, the calcination temperature for homogeneously solubilizing yttria becomes too high and a desirable result cannot be obtained.
  • the powder in which yttria is homogeneously solid-solubilized according to the present invention allows the agglomeration of the powder calcinated as described above to be unbinded by the pulverizing method normally implemented to make easy-to-sinter powder.
  • the pulverizing may be carried out while measuring the particle size of the powder by centrifugal sedimentation for example. The pulverizing is then stopped when the change saturates.
  • the easy-to-sinter high purity raw material powder in which yttria is homogeneously solid-solubilized thus obtained by molding it using normal methods such as die-pressing tape casting, slip casting or extrusion molding and by sintering in relatively low temperature of 1350 to 1550° C or more preferably in 1400 to 1500° C, the sintered body which is fully close and the distribution of the grain size is homogenous can be obtained.
  • the sintering tempeature is too high, the grain of the sintered body abnormally grow and it ends up effecting on the ion conduction characteristics of the solid electrolyte sintered body.
  • the distribution of the grain size of the zirconia sintered body is preferable to be homogenous as much as possible and its coefficient of variation is preferable to be less than 80 % or more preferably to be less than 60 % or further to be less than 40 %.
  • high purity raw material may be used for the raw material used in the production of the powder and the raw material may be refined as necessary in addition to the the method described above.
  • the zirconia sintered body of the present invention thus obtained is characterized in that it has high electrical conductivity in high temperature range and that the temperature change of the electrical conductivity in high temperature range is small.
  • the ion conduction chraracteristics of the solid electrolyte of the solid electrolyte sintered body was evaluated by keeping the solid electrolyte in a certain temperature to measure the resistance value by a normal AC impedance method.
  • the whole resistance of the solid electrolyte is divided into contributions of a bulk resistance which is a resistance component of the solid electrolyte's own and of a component of intergranular resistance caused by the impurities that is maldistributed at the grain boundary.
  • Fig. 1 is a circuit diagram of an equivalent circuit used for parameter fitting, wherein the numeral (1) denotes a solid electrolyte resistance (R SE ), (2) a charge transfer resistance (R CT ), (3) an interface capacitance (Ci), (4) an impedance (Z W1 ), and (5) another impedance (Z W2 ).
  • R SE solid electrolyte resistance
  • R CT charge transfer resistance
  • Ca interface capacitance
  • Z W1 an impedance
  • Z W2 another impedance
  • a powder before calcination in which 3 mol% of yttria had been added obtained by the method in Japanese Patent Application Laid-Open No. 63-185821 was used and was calcinated two times keeping its temperature at 1050° C for 3 hours.
  • the calcinated powder was pulverized for 24 hours using a ball mill. BET specific surface area of the powder after the pulverization was 9.5 m2/g and its average particle size by means of centrifugal sedimentation was 0.2 ⁇ m.
  • the thickness of the zirconia sintered body obtained was about 0.5 mm.
  • platinum elecltrode is attached by vapor deposition, and further on that electrode is appled platinum paste and it was sintered at 1150° C.
  • An electrode with 0.64 cm2 of area was disposed at the lower part of the specimen and another electrode with 0.36 cm2 was disposed at the upper part of the specimen.
  • the effective geometric area of the electrodes was 0.49 cm2 .
  • the zirconia sintered body was cut, a specular polishing was implemented on it and thermal etching was carried out for one hour at 1360° C.
  • the polished surface was observed by a scanning electron microscope.
  • the distributiion of the grain size of the sintered body was found from SEM photographs. Each area on the phto of more than 100 grain arbitrary selected was found and grain size of each grain was found by circular approximation. The average grain size obtained was 0.2 ⁇ m.
  • the grain size of the sintered body obtained was larger than the one in which 3 mol% of yttria was added, its distribution was similarly homogenous.
  • An electrode with 0.64 cm2 of aera was disposed to the anode side and two electrodes with 0.36 cm2 of area respectively was disposed to the cathode side.
  • measurement by means of the AC impedance method was carried out in the above electrode structure. In the measurement of the resistance of the electrode reaction by means of the AC impedance method, the conditions of the two electrodes through which AC is applied is desired to be equal.
  • a relationship of the direct current density and the overpotential in stationary time was found by a normal current interruption method by setting one cathode as a reference electrode.
  • the resistance value obtained from the inclinations or tangent lines of the curves of the direct current density and the overpotential was almost equal with the result of the AC impedance method.
EP19910117124 1990-10-08 1991-10-08 Solid electrolyte sintered body Ceased EP0481332A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2270045A JPH04149064A (ja) 1990-10-08 1990-10-08 固体電解質磁器
JP270045/90 1990-10-08

Publications (2)

Publication Number Publication Date
EP0481332A2 true EP0481332A2 (de) 1992-04-22
EP0481332A3 EP0481332A3 (en) 1993-06-30

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EP19910117124 Ceased EP0481332A3 (en) 1990-10-08 1991-10-08 Solid electrolyte sintered body

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EP (1) EP0481332A3 (de)
JP (1) JPH04149064A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020998A1 (en) * 1993-03-01 1994-09-15 Forskningscenter Risø Solid oxide fuel cell

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2939428A1 (de) * 1978-09-29 1980-04-10 Hitachi Ltd Sauerstoffmessfuehlerkeramik und verfahren zu deren herstellung
GB2054168A (en) * 1979-07-16 1981-02-11 Nissan Motor Method of producing a flat solid electrolyte layer of a flat thin film type oxygen sensor
DE3035072A1 (de) * 1979-09-18 1981-03-19 Ngk Insulators Ltd Feste elektrolyten
EP0034513A1 (de) * 1980-02-08 1981-08-26 COMMISSARIAT A L'ENERGIE ATOMIQUE Etablissement de Caractère Scientifique Technique et Industriel Verfahren zur Herstellung von Festelektrolytkörpern aus stabilisiertem Zirconiumoxid und die nach diesem Verfahren erhaltenen Körper
EP0036786A1 (de) * 1980-03-26 1981-09-30 Ngk Insulators, Ltd. Zirkonoxid-Keramiken und Verfahren zu ihrer Herstellung
EP0218853A1 (de) * 1985-09-06 1987-04-22 Toray Industries, Inc. Verfahren zur Herstellung eines gesinterten Zirkonoxidmaterials
DE3913596A1 (de) * 1988-04-27 1989-11-09 Ngk Spark Plug Co Sauerstoffionen-leitender, fester elektrolyt und verfahren zu seiner herstellung
EP0420284A2 (de) * 1989-09-29 1991-04-03 Nissan Chemical Industries, Limited Herstellung eines Sinterkörpers aus Zirkoniumoxid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2939428A1 (de) * 1978-09-29 1980-04-10 Hitachi Ltd Sauerstoffmessfuehlerkeramik und verfahren zu deren herstellung
GB2054168A (en) * 1979-07-16 1981-02-11 Nissan Motor Method of producing a flat solid electrolyte layer of a flat thin film type oxygen sensor
DE3035072A1 (de) * 1979-09-18 1981-03-19 Ngk Insulators Ltd Feste elektrolyten
EP0034513A1 (de) * 1980-02-08 1981-08-26 COMMISSARIAT A L'ENERGIE ATOMIQUE Etablissement de Caractère Scientifique Technique et Industriel Verfahren zur Herstellung von Festelektrolytkörpern aus stabilisiertem Zirconiumoxid und die nach diesem Verfahren erhaltenen Körper
EP0036786A1 (de) * 1980-03-26 1981-09-30 Ngk Insulators, Ltd. Zirkonoxid-Keramiken und Verfahren zu ihrer Herstellung
EP0218853A1 (de) * 1985-09-06 1987-04-22 Toray Industries, Inc. Verfahren zur Herstellung eines gesinterten Zirkonoxidmaterials
DE3913596A1 (de) * 1988-04-27 1989-11-09 Ngk Spark Plug Co Sauerstoffionen-leitender, fester elektrolyt und verfahren zu seiner herstellung
EP0420284A2 (de) * 1989-09-29 1991-04-03 Nissan Chemical Industries, Limited Herstellung eines Sinterkörpers aus Zirkoniumoxid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
APPLIED PHYSICS A. SOLIDS AND SURFACES vol. 50, no. 5, May 1990, BERLIN DE pages 449 - 462 S.P.S.BADWAL 'Yttrria Tetragonal Zirconia Polycrystalline Electrolytes for Solid State Electrochemical Cells' *
SOLID STATE IONICS. vol. 3/4, 1981, AMSTERDAM NL pages 489 - 493 K. KOBAYSASHI ET AL 'PHASE CHANGE AND MECHANICAL PROPERTIES OF ZrO2-Y2O3 SOLID ELECTROLYTE AFTER AGEING' *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020998A1 (en) * 1993-03-01 1994-09-15 Forskningscenter Risø Solid oxide fuel cell
US5591537A (en) * 1993-03-01 1997-01-07 Forskningscenter RIS.O slashed. Solid oxide fuel cell

Also Published As

Publication number Publication date
EP0481332A3 (en) 1993-06-30
JPH04149064A (ja) 1992-05-22

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